Titanium Dioxide Particles Modified by Salicylic Acid and Arginine and Their Photocatalytic Reaction on Oil-Water Interface

doi:10.15541/jim20150423

Abstract

Abstract:

Salicylate acid and arginine-modified TiO₂particles (TiO₂-SA/Arg) were successfully fabricated by impregnation approach using salicylate acid and arginine grafted onto the surface of nano-TiO₂. The morphology, structure and properties of modified samples were characterized by means of Fourier-transform infrared spectroscope (FT-IR), X-ray photoelectron spectroscope (XPS), thermogravimetry ansysis (TGA), ultraviolet-visible diffuse reflectance spectroscope (UV-Vis DRS), scanning electron microscope (SEM), high-resolution transmission electron microscope (HRTEM), surface contact angle analysis, and particle size distribution analysis. The nitrobenzene adsorption capacity and the ability to be attracted to the oil-water interface of the modified samples were also confirmed. Results revealed that salicylate acid and arginine were modified to TiO₂ surface by chelation and bridging structure, respectively. The modified TiO₂ had better hydrophobicity, dispersion properties and adsorption capacity of nitrobenzene than the unmodified TiO₂. A stable O/W Pickering emulsion was successfully fabricated via the photocatalyst stably adsorbed to oil-water interface. Nitrobenzene in Pickeing emulsion-based photocatalytic reaction system, stabilized by modified photocatalyst, showed a higher removal rate of high concentrations of nitrobenzene than the suspension system.

Key words: surface modification, surface structure, photocatalysis, Pickering emulsion

CLC Number:

TQ174

LI Lei, ZHANG Qiao-Ling, FAN Hong-Lei, LIU You-Zhi, WEI Bing, FENG Yu-Jie. Titanium Dioxide Particles Modified by Salicylic Acid and Arginine and Their Photocatalytic Reaction on Oil-Water Interface[J]. Journal of Inorganic Materials, 2016, 31(4): 413-420.

Figures/Tables 10

Fig. 1 FT-IR spectra of different samples (a) Arg; (b) SA; (c) TiO2; (d) TiO2-SA/Arg before irradiation; (e) TiO2- SA/Arg after1h irradiation; (f) TiO2-SA/Arg after 3h irradiation; (f) TiO2-SA/Arg after 24 h irradiation

Fig. 2 C1s (a), N1s (b) and O1s (c) XPS spectra of modified samples

Fig. 3 TG curve of samples after modification

Fig. 4 Contact angles of photocatalyst (a) TiO2; (b) TiO2-SA/Arg; (c) TiO2-SA/Arg after irradiation

Fig. 5 SEM and HRTEM images of photocatalysts (a,d,g) TiO2; (b,e,h) TiO2-SA/Arg; (c,f,i) TiO2-SA/Arg after irradiation

Fig. 6 UV-Vis diffuse reflectance spectra of samples

Fig. 7 Adsorption isotherms of NB measured in aqueous solutions

Fig. 8 Stability of Pickeing emulsion stabilized by TiO2- SA/Arg

Fig. 9 Curves of photocatalytic degradation of NB (a) Blank; (b) TiO2 in suspension; (c) TiO2-SA/Arg in suspension; (d) 2.66wt% TiO2-SA/Arg in emulsion; (e) 9.85wt% TiO2-SA/Arg in emulsion; (f) 5.18wt% TiO2-SA/Arg in emulsion. Inset is the HPLC curves of emulsion

Fig.10 Schematic of a highly efficient Pickering emulsion- based photocatalytic system formed by self-assembling TiO2 particles co-modified by salicylic acid and arginine at water/oil interface

References 28

[1]	WANG BIN, ZHANG GUANG-XIN, ZHENG SHUI-LIN, et al.Effect of calcination temperature on crystal structure and photocatalytic property of TiO2/diatomite nanoparticles.Journal of Inorganic Materials, 2014, 29(4): 382-386.
[2]	LIU GUO-CONG, LI HAI-BIN, DONG HUI.Ultrasonic-hydrothermal synthesis and photocatalytic activities of La-doped mesoporous TiO2 microspheres.Journal of Inorganic Materials, 2011, 26(7): 739-746.
[3]	ZHANG QING-HONG.Progress on TiO2-based nanomaterials and Its utilization in the clean energy technology.Journal of Inorganic Materials, 2012, 27(1): 1-10.
[4]	HUGO I D L, BENITO S R. Photocatalytic Technologies. Beijing: Science Press, 2010: ix-xii.
[5]	NSIB M F, MAAYOUFI A, MOUSSA N J, et al.TiO2 modified by salicylic acid as a photocatalyst for the degradation of monochlorobenzene via Pickering emulsion way.Photochem. Photobiol. A: Chem., 2013, 251: 10-17.
[6]	RAMSDEN W. Separation of solids in the surface-layers of solutions and suspensions. Proc. R. Soc. Lon., 1903-1904, 72: 156-164.
[7]	PICKERING S U.Emulsions.J. Am. Chem. Soc., 1907, 91: 2001-2021.
[8]	LAGALY G, REESE M, ABEND S.Smectites as colloidal stabilizers of emulsions II: Rheological properties of smectite-laden emulsions.Appl. Clay. Sci. 1999, 14: 279-298.
[9]	TARIMALA S, DAI L L.Structure of microparticles in solid- stabilized emulsions.Langmuir, 2004, 20: 3490-3494.
[10]	BINKS B P.Particles as surfactants-similarities and differencesCurr. Opin. Colloid Interface Sci., 2002, 7: 21-41.
[11]	YANG F, WANG J, LAN Q, et al.Research progress on Pickering emulsions. Prog. Chem., 2009, 21(7): 1418-1426.
[12]	WU WEI, GAO SHUANG, TU WEI-XIA, et al.Intensified photocatalytic degradation of nitrobenzene by Pickering emulsion of ZnO nanoparticles.Particuology, 2010, 8(5): 453-457.
[13]	NAKATO T, UEDA H, HASHIMOTO S, et al.Pickering emulsions prepared by layered niobate K4Nb6O17 intercalated with organic cations and photocatalytic dye decomposition in the emulsions.ACS Appl. Mater. Interfaces, 2012, 4(8): 4338-4347.
[14]	ZHAI WAN-YING, LI GAI-PING, YU PING, et al.Silver phosphate/carbon nanotube-stabilized Pickering emulsion for highly efficient photocatalysis.J. Phys. Chem. C, 2013, 117: 15183-15191.
[15]	CLARIZIA L, SPASIANO D, DI SOMMA I, et al.Copper modified- TiO2 catalysts for hydrogen generation through photoreforming of organics. a short review.Int. J. Hydrogen Energ., 2014, 39(30): 16812-16831.
[16]	LÜ YU-ZHEN, ZHANG SHENG-NAN, DU YUE-FAN, et al.Effect of oleic acid surface modification on dispersibility of TiO2 nanoparticles in transformer oils.Journal of Inorganic Materials, 2013, 28(6): 594-598.
[17]	YAO CHAO, GAO GUO-SHENG, LIN XI-PING, et al.Surface modification of nanosized TiO2 with silane coupling reagent.Journal of Inorganic Materials, 2006, 21(2): 315-321.
[18]	TAI HUI-LING, JIANG YA-DONG, XIE GUANG-ZHONG, et al.Fabrication and gas sensitivity study of polyprrole/titanium oxide composite thin films.Journal of Inorganic Materials, 2007, 22(3): 524-528.
[19]	RAZA M, BACHINGER A, ZAHN N, et al.Interaction and UV-stability of various organic capping agents on the surface of anatase nanoparticles.Materials, 2014, 7: 2890-2912.
[20]	WANG NAN, ZHU LI-HUA, DENG KE-JIAN, et al.Visible light photocatalytic reduction of Cr(VI) on TiO2 in situ modified with small molecular weight organic acids.Appl. Catal. B-Environ., 2010, 95: 400-407.
[21]	DOBSON K D, MCQUILLAN A J.In situ infrared spectroscopic analysis of the adsorption of aliphatic carboxylic acids to TiO2, ZrO2, Al2O3, and Ta2O5 from aqueous solutions.Spectrochim. Acta A, 1999, 55: 1395-1405.
[22]	LI SHUN-XING, ZHENG FENG-YING, CAI SHU-JIE, et al.A visible light assisted photocatalytic system for determination of chemical oxygen demand using 5-sulfosalicylic acid in situ surface modified titanium dioxide.Sensor. Actuat. B-Chem., 2013, 188: 280-285.
[23]	LI SUNG-XING, ZHENG FENG-YING, CAI WEN-LIAN, et al.Surface modification of nanometer size TiO2 with salicylic acid for photocatalytic degradation of 4-nitrophenol.J. Hazard. Mater., 2008, B135: 431-436.
[24]	CROPEK D, KEMME P A, MAKAROVA O V, et al.Selective photocatalytic decomposition of nitrobenzene using surface modified TiO2 nanoparticles.J. Phys. Chem. C, 2008, 112: 8311-8318.
[25]	HUANG H Y, ZHOU J H, LIU H L, et al.Selective photoreduction of nitrobenzene to aniline on TiO2 nanoparticles modified with amino acid.J. Hazard. Mater., 2010, 178: 994-998.
[26]	NAKAYAMA N, HAYASHI T.Preparation of TiO2 nanoparticles surface-modified by both carboxylic acid and amine: dispersibility and stabilization in organic solvents.Colloid Surf. A-Physicochem. Eng. Asp., 2008: 317(1/2/3): 543-550.
[27]	NAKAMOTO K.Infrared and Raman Spectra of Inorganic and Coordination Compounds. New York: Wiley, 1978: 232-233.
[28]	ZHANG QIAO-LING, LI LEI, LIU YOU-ZHI, et al.Grafting dynamics, structures and properties of nano TiO2-SA photocatalytic materials.Acta Phys. -Chim. Sin., 2015, 31(6): 1015-1024.